US6117354A - Piezoelectric ceramic composition - Google Patents

Piezoelectric ceramic composition Download PDF

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Publication number
US6117354A
US6117354A US09/312,247 US31224799A US6117354A US 6117354 A US6117354 A US 6117354A US 31224799 A US31224799 A US 31224799A US 6117354 A US6117354 A US 6117354A
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piezoelectric ceramic
sup
ceramic composition
manganese
mnco
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US09/312,247
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Masahiko Kimura
Akira Ando
Tadahiro Minamikawa
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/80Constructional details
    • H10N30/85Piezoelectric or electrostrictive active materials
    • H10N30/853Ceramic compositions

Definitions

  • the present invention relates to a piezoelectric ceramic composition, and more particularly to a piezoelectric ceramic composition useful as a material for producing piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators.
  • Piezoelectric ceramic compositions predominantly comprising lead titanate zirconate (Pb(Ti x Zr 1-x , O 3 ) or lead titanate (PbTiO 3 ) have been widely used for the production of piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators.
  • Piezoelectric ceramic compositions predominantly comprising lead titanate zirconate or lead titanate are generally produced by use of lead oxides, which cause a reduction in homogeneity of products due to evaporation of lead oxides.
  • piezoelectric ceramic compositions predominantly comprising a layered bismuth compound represented by (Sr 1-x M x )Bi 2 Nb 2 O 9 contain no lead oxide and therefore do not introduce this type of problem.
  • piezoelectric ceramic compositions predominantly comprising a layered bismuth compound have a small electromechanical coupling coefficient kt and therefore have not yet been widely used in practice.
  • the present inventors conducted earnest studies to improve electromechanical coupling coefficient kt of a piezoelectric ceramic composition predominantly comprising a layered bismuth compound to thereby provide a piezoelectric ceramic composition which, when used as a material for the production of piezoelectric ceramic elements, exhibits a practical, acceptable electromechanical coupling coefficient kt value (more than 10%).
  • the effect of the present invention is particularly excellent when M in the formula is at least one element selected from Ca and Ba.
  • Ca and Ba may both be contained as M.
  • piezoelectric ceramic samples were prepared according to the following method.
  • the particle-size-regulated powder was molded at 1000 kg/cm 2 into a disk having a diameter of 12.5 mm and a thickness of 1 mm, and the disk was fired in air to thereby form a ceramic disk.
  • the disk was subjected to a polarization treatment by the application of a DC voltage of 5-20 kV/mm for 10-30 minutes in a 150° C.-200° C. insulating oil to thereby obtain a piezoelectric ceramic serving as a sample.
  • the sample was subjected to measurement of density, resistivity, and electromechanical coupling coefficient kt. The results are shown in Table 1.
  • each of sample Nos. 2, 3, 4, 7, 8, 11, 12, 16 and 19, which fall within the scope of the present invention has an improved electromechanical coupling coefficient kt as compared with sample Nos. 1, 5, 6, 9, 10, 13, 14, 15, 17, 18, 20 and 21, which fall outside the scope of the present invention.
  • electromechanical coupling coefficient kt of the piezoelectric ceramic composition which predominantly comprises a layered bismuth compound can be improved, and a piezoelectric ceramic composition useful as a material for piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators can be advantageously produced.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

A piezoelectric ceramic composition which contains a ceramic compound and manganese. The ceramic compound serves as a primary component and is represented by formula (Sr1-xMx)Bi2Nb2O9. In the formula, M represents a divalent metal element and x satisfies 0</=x</=0.3. Manganese is contained in an amount of 1.0 wt. % or less (0 being excluded) as MnCO3.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a piezoelectric ceramic composition, and more particularly to a piezoelectric ceramic composition useful as a material for producing piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators.
2. Background Art
Piezoelectric ceramic compositions predominantly comprising lead titanate zirconate (Pb(Tix Zr1-x, O3) or lead titanate (PbTiO3) have been widely used for the production of piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators. Piezoelectric ceramic compositions predominantly comprising lead titanate zirconate or lead titanate are generally produced by use of lead oxides, which cause a reduction in homogeneity of products due to evaporation of lead oxides. In contrast, piezoelectric ceramic compositions predominantly comprising a layered bismuth compound represented by (Sr1-x Mx)Bi2 Nb2 O9 contain no lead oxide and therefore do not introduce this type of problem.
However, piezoelectric ceramic compositions predominantly comprising a layered bismuth compound have a small electromechanical coupling coefficient kt and therefore have not yet been widely used in practice.
SUMMARY OF THE INVENTION
In view of the foregoing, the present inventors conducted earnest studies to improve electromechanical coupling coefficient kt of a piezoelectric ceramic composition predominantly comprising a layered bismuth compound to thereby provide a piezoelectric ceramic composition which, when used as a material for the production of piezoelectric ceramic elements, exhibits a practical, acceptable electromechanical coupling coefficient kt value (more than 10%).
The piezoelectric ceramic composition according to the present invention comprises a ceramic compound and manganese, wherein the ceramic compound serves as a primary component and is represented by formula (Sr1-x Mx)Bi2 Nb2 O9 wherein M represents a divalent metal element and x satisfies 0≦x≦0.3, and the manganese is contained in an amount of 1.0 wt. % or less (0 being excluded) calculated as MnCO3. The aforementioned parameter x is limited to 0-0.3 because if x falls outside the range, the effect of the present invention is not appreciable and an electromechanical coupling coefficient kt which enables the piezoelectric ceramic composition to serve in practice cannot be obtained. The amount of manganese is limited to 1.0% by weight or less (0 being excluded) as MnCO3 because when the manganese content falls outside the specified range, polarizable ceramics cannot be obtained.
Moreover, the effect of the present invention is particularly excellent when M in the formula is at least one element selected from Ca and Ba. Ca and Ba may both be contained as M.
The above and other objects, features, and advantages of the present invention will be more clearly understood from the below-described description of preferred embodiments of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention will next be described in more detail.
A variety of piezoelectric ceramic samples were prepared according to the following method.
Starting raw materials, SrO, Bi2 O3, Nb2 O5, CaO, BaO and MnCO3 were provided and were weighed so as to form a compound of the formula (Sr1-x Mx)Bi2 Nb2 O9 wherein M represents a divalent metal element and x satisfies 0≦x≦0.3, followed by wet-mixing for about four hours by use of a ball mill. The resultant mixture was dried and then calcined at 700-900° C. Subsequently, the dried mixture was roughly crushed, wet-milled with an appropriate amount of an organic binder for four hours by use of a ball mill and passed through a 40-mesh sieve to thereby regulate the particle size of the milled powder. Subsequently, the particle-size-regulated powder was molded at 1000 kg/cm2 into a disk having a diameter of 12.5 mm and a thickness of 1 mm, and the disk was fired in air to thereby form a ceramic disk. After silver electrodes were formed on the surfaces (both main surfaces) of the ceramic disk by applying and burning a silver paste through a customary method, the disk was subjected to a polarization treatment by the application of a DC voltage of 5-20 kV/mm for 10-30 minutes in a 150° C.-200° C. insulating oil to thereby obtain a piezoelectric ceramic serving as a sample. The sample was subjected to measurement of density, resistivity, and electromechanical coupling coefficient kt. The results are shown in Table 1.
              TABLE 1                                                     
______________________________________                                    
Sample              MnCo.sub.3                                            
                          Density                                         
                                 Resistivity                              
                                        kt                                
No.    M     x      (wt %)                                                
                          (g/cm.sup.3)                                    
                                 (Ω · cm)                  
                                        (%)                               
______________________________________                                    
*1     --    0      0     6.75   2.0 × 10.sup.11                    
                                        8.5                               
2      --    0      0.1   7.05   4.0 × 10.sup.13                    
                                        20.5                              
3      --    0      0.5   6.96   6.0 × 10.sup.12                    
                                        17.6                              
4      --    0      1.0   6.80   4.0 × 10.sup.12                    
                                        16.8                              
*5     --    0      1.1   6.67   2.0 × 10.sup.10                    
                                        Not polarizable                   
*6     Ca    0.1    0     6.80   2.0 × 10.sup.11                    
                                        8.8                               
7      Ca    0.1    0.1   7.08   5.0 × 10.sup.13                    
                                        22.9                              
8      Ca    0.1    1.0   6.70   4.0 × 10.sup.12                    
                                        19.7                              
*9     Ca    0.1    1.1   6.65   2.0 × 10.sup.10                    
                                        Not polarizable                   
*10    Ca    0.3    0     6.65   2.0 × 10.sup.11                    
                                        8.5                               
11     Ca    0.3    0.1   6.98   4.0 × 10.sup.13                    
                                        17.9                              
12     Ca    0.3    1.0   6.67   2.0 × 10.sup.12                    
                                        17.6                              
*13    Ca    0.3    1.1   6.44   1.0 × 10.sup.10                    
                                        Not polarizable                   
*14    Ca    0.4    0.1   6.26   7.0 × 10.sup.9                     
                                        9.6                               
*15    Ba    0.1    0     6.85   2.0 × 10.sup.11                    
                                        8.7                               
16     Ba    0.1    0.1   7.07   3.0 × 10.sup.13                    
                                        21.9                              
*17    Ba    0.1    1.1   6.65   1.0 × 10.sup.10                    
                                        Not polarizable                   
*18    Ba    0.3    0     6.67   9.0 × 10.sup.10                    
                                        8.4                               
19     Ba    0.3    0.1   7.00   1.0 × 10.sup.13                    
                                        20.9                              
*20    Ba    0.3    1.1   6.47   2.0 × 10.sup.10                    
                                        Not polarizable                   
*21    Ba    0.4    0.1   6.31   8.0 × 10.sup.9                     
                                        9.1                               
______________________________________                                    
Samples marked with * fall outside the scope of invention.
As is apparent from Table 1, each of sample Nos. 2, 3, 4, 7, 8, 11, 12, 16 and 19, which fall within the scope of the present invention, has an improved electromechanical coupling coefficient kt as compared with sample Nos. 1, 5, 6, 9, 10, 13, 14, 15, 17, 18, 20 and 21, which fall outside the scope of the present invention.
According to the present invention, electromechanical coupling coefficient kt of the piezoelectric ceramic composition which predominantly comprises a layered bismuth compound can be improved, and a piezoelectric ceramic composition useful as a material for piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators can be advantageously produced.

Claims (4)

What is claimed is:
1. A piezoelectric ceramic composition comprising a ceramic compound and manganese, wherein the ceramic compound is the primary component and is represented by the formula (Sr1-x Mx)Bi2 Nb2 O9 wherein M represents at least one divalent metal element and 0≦x≦0.3, and the manganese is in an amount of 1.0 wt. % or less (0 being excluded) calculated as MnCO3.
2. A piezoelectric ceramic composition according to claim 1, wherein M is at least one of Ca and Ba.
3. A piezoelectric ceramic composition according to claim 1, wherein M is Ca and the manganese amount is 0.1 to 1.0 wt. % calculated as MnCO3.
4. A piezoelectric ceramic composition according to claim 1, wherein M is Ba and the manganese amount is 0.1 to 1.0 wt. % calculated as MnCO3.
US09/312,247 1998-05-20 1999-05-14 Piezoelectric ceramic composition Expired - Lifetime US6117354A (en)

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JP15664898A JP3399364B2 (en) 1998-05-20 1998-05-20 Piezoelectric ceramic composition
JP10-156648 1998-05-20

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2353524A (en) * 1999-08-26 2001-02-28 Murata Manufacturing Co Piezoelectric ceramic composition and device
US6258291B1 (en) * 1999-02-08 2001-07-10 Murata Manufacturing Co., Ltd Piezoelectric ceramic composition and piezoelectric ceramic device using the same
US6383411B1 (en) * 1999-08-26 2002-05-07 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition and piezoelectric ceramic device using the same
US6685850B2 (en) * 2000-07-28 2004-02-03 Tdk Corporation Piezoelectric ceramic material
US6764609B2 (en) 2001-10-11 2004-07-20 Matsushita Electric Industrial Co., Ltd. Piezoelectric ceramic composition and piezoelectric element using the same
US20080169445A1 (en) * 2005-09-30 2008-07-17 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition and piezoelectric component
US20110133608A1 (en) * 2008-03-18 2011-06-09 Kyocera Corporation Piezoelectric ceramic and piezoelectric element using the same
US20110241483A1 (en) * 2010-03-31 2011-10-06 Tdk Corporation Piezoelectric composition, piezoelectric ceramic, transducer, and ultrasonic motor

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CN109692963B (en) * 2018-12-18 2022-06-10 宁波中杭磁材有限公司 Preparation method of neodymium iron boron magnet with corrosion-resistant coating attached to surface
CN109604618B (en) * 2018-12-18 2022-06-10 宁波中杭磁材有限公司 Preparation method of neodymium iron boron magnet with wear-resistant coating attached to surface
CN119285356B (en) * 2024-12-16 2025-02-14 湖南省美程陶瓷科技有限公司 Piezoelectric ceramic material with high Curie temperature and high piezoelectric coefficient and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4877398A (en) * 1972-01-24 1973-10-17
JPS4878500A (en) * 1972-01-26 1973-10-22

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
DE4223186A1 (en) * 1992-07-15 1994-01-20 Hoechst Ceram Tec Ag Sinterable offset at low temperatures for the production of piezoelectric, ceramic shaped bodies and shaped bodies produced therefrom by sintering
EP0581481B1 (en) * 1992-07-31 1997-04-23 Toyota Jidosha Kabushiki Kaisha Bismuth layer compound
US5762816A (en) * 1995-11-14 1998-06-09 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4877398A (en) * 1972-01-24 1973-10-17
JPS4878500A (en) * 1972-01-26 1973-10-22

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258291B1 (en) * 1999-02-08 2001-07-10 Murata Manufacturing Co., Ltd Piezoelectric ceramic composition and piezoelectric ceramic device using the same
GB2353524A (en) * 1999-08-26 2001-02-28 Murata Manufacturing Co Piezoelectric ceramic composition and device
GB2353524B (en) * 1999-08-26 2001-08-08 Murata Manufacturing Co Piezoelectric ceramic composition and piezoelectric ceramic device using the same
US6383411B1 (en) * 1999-08-26 2002-05-07 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition and piezoelectric ceramic device using the same
US6423244B1 (en) 1999-08-26 2002-07-23 Murata Manufacturing Co. Ltd. Piezoelectric ceramic composition and piezoelectric ceramic device using the same
US6685850B2 (en) * 2000-07-28 2004-02-03 Tdk Corporation Piezoelectric ceramic material
US6764609B2 (en) 2001-10-11 2004-07-20 Matsushita Electric Industrial Co., Ltd. Piezoelectric ceramic composition and piezoelectric element using the same
US20080169445A1 (en) * 2005-09-30 2008-07-17 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition and piezoelectric component
US7510669B2 (en) * 2005-09-30 2009-03-31 Murata Manufacturing Co., Ltd. Piezoelectric ceramic composition and piezoelectric component
US20110133608A1 (en) * 2008-03-18 2011-06-09 Kyocera Corporation Piezoelectric ceramic and piezoelectric element using the same
US8643255B2 (en) * 2008-03-18 2014-02-04 Kyocera Corporation Piezoelectric ceramic and piezoelectric element using the same
US20110241483A1 (en) * 2010-03-31 2011-10-06 Tdk Corporation Piezoelectric composition, piezoelectric ceramic, transducer, and ultrasonic motor
US8564180B2 (en) * 2010-03-31 2013-10-22 Tdk Corporation Piezoelectric composition, piezoelectric ceramic, transducer, and ultrasonic motor

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Publication number Publication date
KR19990088364A (en) 1999-12-27
DE19922955A1 (en) 1999-11-25
JP3399364B2 (en) 2003-04-21
KR100296933B1 (en) 2001-10-18
CN1238316A (en) 1999-12-15
DE19922955C2 (en) 2002-12-05
CN1104396C (en) 2003-04-02
JPH11322426A (en) 1999-11-24

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